Oxalates, Removal

Pentaerythritol.47 To a mixture of 18.5 g. of calcium hydroxide and 75 g. of formaldehyde in 500 cc. of water is slowly added 22 g. of acetaldehyde. The temperature of the mixture is maintained at 15° during the addition of the acetaldehyde and then gradually raised to 45°. The calcium is precipitated with oxalic acid, the calcium oxalate removed by filtration, and the filtrate evaporated to dryness under reduced pressure. The residue is taken up in 200 cc. of hot ethanol, and the resulting solution allowed to cool. The pentaerythritol which separates weighs 50 g. (73.5% of the theoretical amount) and melts at 258°. Pure pentaerythritol melts at 260°.46 ... 

Extraction of Sedimentary Constituents. The proportion of the total concentration of Fe, Mn and Zn removed from the estuarine sediments by the different extractants varied widely among sampling stations (Table II). Hydrochloric acid, acetic acid and ammonium oxalate removed a similar proportion of total Zn from all sediments. Concentrations of Zn well above detection limits were also fo-iind in the ammonia, hydroxyl-amine and ammonium acetate extracts. The quantity of Zn removed from oxidized sediments by the latter two extractants was significantly greater than reported in previous studies in which reduced sediments were extracted ( ). 

The gas is passed through caustic soda solution to remove any sulphur dioxide or carbon dioxide produced in side reactions. Carbon monoxide is also obtained when an ethanedioate (oxalate) is heated with concentrated sulphuric acid ... 

Urea oxalate is also sparingly soluble in amyl alcohol and since urea is soluble in this alcohol, the property may be utilised in separating urea from mixtures. An aqueous extract of the mixture is rendered slightly alkaline with sodium hydroxide solution and extracted with ether this removes all the basic components, but not urea. The residual aqueous solution is extracted with amyl alcohol (to remove the urea) upon adding this extract to a solution of oxalic acid in amyl alcohol crystalline urea oxalate is precipitated. 

The only reported industrial appHcation for Fep2 is its use in mst removal solutions based on oxalic acid (6). The anhydrous salt is commercially available in 100 g to 5 kg lots from Advance Research Chemicals, Aldrich Chemicals, Cerac, Johnson/Matthey, PCR, and other suppHers in the United States. As of 1993, the prices varied between 500 to 700/kg. 

In order to make an efficient Y202 Eu ", it is necessary to start with weU-purifted yttrium and europium oxides or a weU-purifted coprecipitated oxide. Very small amounts of impurity ions, particularly other rare-earth ions, decrease the efficiency of this phosphor. Ce " is one of the most troublesome ions because it competes for the uv absorption and should be present at no more than about one part per million. Once purified, if not already coprecipitated, the oxides are dissolved in hydrochloric or nitric acid and then precipitated with oxaflc acid. This precipitate is then calcined, and fired at around 800°C to decompose the oxalate and form the oxide. EinaHy the oxide is fired usually in air at temperatures of 1500—1550°C in order to produce a good crystal stmcture and an efficient phosphor. This phosphor does not need to be further processed but may be milled for particle size control and/or screened to remove agglomerates which later show up as dark specks in the coating. 

Marble Polishing. Oxahc acid is used for marble polishing especially in Italy. It not only removes iron veins by forming water-soluble iron oxalate, but also serves as a polishing auxihary. 

Millet Jelly Production. Starch powder is heated together with oxahc acid and hydrolyzed to produce millet jelly. Oxahc acid functions as a hydrolysis catalyst, and is removed from the product as calcium oxalate. This apphcation is carried out in Japan. 

The central carbon atom is derived from an aromatic aldehyde or a substance capable of generating an aldehyde during the course of the condensation. Malachite green is prepared by heating benzaldehyde under reflux with a slight excess of dimethyl aniline in aqueous acid (Fig. 2). The reaction mass is made alkaline and the excess dimethylaniline is removed by steam distillation. The resulting leuco base is oxidized with freshly prepared lead dioxide to the carbinol base, and the lead is removed by precipitation as the sulfate. Subsequent treatment of the carbinol base with acid produces the dye, which can be isolated as the chloride, the oxalate [2437-29-8] or the zinc chloride double salt [79118-82-4]. 

Ethylenediamine tetraacetic acid (EDTA) [60-00-4] (Sequestrene), an anticoagulent at 1 mg of the disodium salt per mL blood, complexes with and removes calcium, Ca ", from the blood. Oxalate, citrate, and fluoride ions form insoluble salts with Ca " and chelate calcium from the blood. Salts containing these anticoagulants include lithium oxalate [553-91-3] 1 mg/mL blood sodium oxalate [62-76-0]2 mg/mL blood ... 

Dimethyl carbonate [616-38-6] and dimethyl oxalate [553-90-2] are both obtained from carbon monoxide, oxygen, and methanol at 363 K and 10 MPa (100 atm) or less. The choice of catalyst is critical cuprous chloride (66) gives the carbonate (eq. 20) a palladium chloride—copper chloride mixture (67,68) gives the oxalate, (eq. 21). Anhydrous conditions should be maintained by removing product water to minimize the formation of by-product carbon dioxide. 

Chemical Treatment. The most iavolved regeneration technique is chemical treatment (20) which often follows thermal or physical treatment, after the char and particulate matter has been removed. Acid solution soaks, glacial acetic acid, and oxalic acid are often used. The bed is then tinsed with water, lanced with air, and dried ia air. More iavolved is use of an alkaline solution such as potassium hydroxide, or the combination of acid washes and alkaline washes. The most complex treatment is a combination of water, alkaline, and acid washes followed by air lancing and dryiag. The catalyst should not be appreciably degraded by the particular chemical treatment used. 

Dry air is blown through the solution to remove the excess of ammonia, and the solution is then dissolved in its own volume of absolute alcohol. A sample of this solution is titrated with standard oxalic acid, litmus being used as an outside indicator (Note 3). The amount of oxalic acid (Note 4) necessary to form the acid salt is placed in a large evaporating dish and dissolved in 4 1. of 95 per cent alcohol. The amine solution is then slowly run into the acid with constant stirring. During the addition of the last half of the amine solution, the container must be cooled in order to avoid the formation of the neutral oxalate,... 

Cellulose for chromatography is purified by sequential washing with chloroform, ethanol, water, ethanol, chloroform and acetone. More extensive purification uses aqueous ammonia, water, hydrochloric acid, water, acetone and diethyl ether, followed by drying in a vacuum. Trace metals can be removed from filter paper by washing for several hours with O.IM oxalic or citric acid, followed by repeated washing with distilled water. 

Tri-n-octylphosphine oxide [78-50-2] M 386.7, m 59.5-60°, pK jt <0. Mason, McCarty and Peppard [J Inorg Nuclear Chem 24 967 7962] stirred an O.IM solution in benzene with an equal volume of 6M HCl at 40° in a sealed flask for 48h, then washed the benzene solution successively with water (twice), 5% aq Na2C03 (three times) and water (six times). The benzene and water were then evaporated under reduced pressure at room temperature. Zingaro and White [J Inorg Nucl Chem 12 315 7960] treated a pet ether solution with aqueous KMn04 (to oxidise any phosphinous acids to phosphinic acids), then with sodium oxalate, H2SO4 and HCl (to remove any manganese compounds). The pet ether solution was slurried with activated alumina (to remove phosphinic acids) and recrystd from pet ether or cyclohexane at -20°. It can also be crystd from EtOH. 

Preparation. The mother liquors from strychnine manufacture are concentrated and the alkaloids precipitated as neutral oxalates. The precipitate is dried and extracted with dry alcohol in which the strychnine salt is the more soluble. The less soluble salt dissolved in water is decolorised with charcoal, the alkaloid regenerated with ammonia and purified by crystallisation as the sulphate. According to Saunders, pure brucine may be obtained by slow crystallisation from a solution of the pure hydrochloride in alcoholic ammonia. A method of separation depending on the greater solubility in water of strychnine hydriodide was employed by Shenstone, whilst others have made use of the sparing solubility of strychnine chromate for the removal of small quantities of this alkaloid from brucine. For a large scale process see Schwyzer. ... 

Androst-4-ene-3,17-dione. Testosterone (0.58 g, 2 mmoles) is dissolved in a solution prepared from 3 ml of benzene, 3 ml of dimethyl sulfoxide, 0.16 ml (2 mmoles) of pyridine and 0.08 ml (1 mmole) of trifluoroacetic acid. After addition of 1.24 g (6 mmoles) of dicyclohexylcarbodiimide, the sealed reaction flask is kept overnight at room temperature. Ether (50 ml) is added followed by a solution of 0.54 g (6 mmoles) of oxalic acid in 5 ml of methanol. After gas evolution has ceased ( 30 min) 50 ml of water is added and the insoluble dicyclohexylurea is removed by filtration. The organic phase is then extracted twice with 5 % sodium bicarbonate and once with water, dried over sodium sulfate and evaporated to a crystalline residue (0.80 g) which still contains a little dicyclohexylurea. Direct crystallization from 5 ml of ethanol gives androst-4-ene-3,17-dione (0.53 g, 92%) in two crops, mp 169-170°. 

During the preparation of the dihalo-(usually dibromo) 20-ketopregnanes, other reactive sites must be protected (e.g., addition of bromine to the A -double bond, ketal formation with a 3-ketone). An elegant method which avoids such problems has been devised by the Upjohn group in their studies on the conversion of 11-ketoprogesterone to hydrocortisone. The former is reacted with ethyl oxalate at C-2 and C-21, then addition of three moles of bromine gives a 2,21,21-tribromide. Alkaline rearrangement produces the side chain unsaturated acid, and the bromine at C-2 is subsequently removed with zinc. 

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